CN109575370A - A kind of preparation method of amination β-CD/PTCA functionalization graphene composite material - Google Patents
A kind of preparation method of amination β-CD/PTCA functionalization graphene composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 41
- KKJUPNGICOCCDW-UHFFFAOYSA-N 7-N,N-Dimethylamino-1,2,3,4,5-pentathiocyclooctane Chemical compound CN(C)C1CSSSSSC1 KKJUPNGICOCCDW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 title claims abstract description 28
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000005576 amination reaction Methods 0.000 title claims abstract description 20
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009825 accumulation Methods 0.000 abstract description 2
- 239000000908 ammonium hydroxide Substances 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract 1
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 229920000858 Cyclodextrin Polymers 0.000 description 8
- 239000001116 FEMA 4028 Substances 0.000 description 4
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 4
- 229960004853 betadex Drugs 0.000 description 4
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
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Abstract
The invention discloses a kind of preparation methods of amination β-CD/PTCA functionalization graphene composite material, it is that graphene oxide GO PTCA is first passed through into π-π effect removing, reduce GO reuniting effect due to caused by pi-pi accumulation, increase the interlamellar spacing of GO, it obtains the GO-PTCA of functionalization, then under the conditions of existing for the ammonium hydroxide and hydrazine hydrate, GO-PTCA is restored, rGO-PTCA is obtained, then EDC and NHS is recycled as crosslinking agent and makes NH2Composite material rGO-PTCA-CD is made by amido bond covalent bonding in the carboxyl on amino and rGO-PTCA on-β-CD.Chemical property detection display, composite material rGO-PTCA-CD prepared by the present invention have better electronic transmission performance, can be applied to for fields such as supercapacitor, electrochemical sensor, lithium ion battery, nano material and hydrogen storages.
Description
Technical field
The present invention relates to a kind of preparations of amination β-CD/PTCA functionalization graphene composite material (rGO-PTCA-CD)
Method；Present invention simultaneously relates to the amidation process of the composite material, belong to technical field of composite materials.
Background technique
Graphene is a kind of two-dimensional carbon nanomaterial, has been widely used for supercapacitor, electrochemical sensor, lithium
The fields such as ion battery, nano material and hydrogen storage.But since the π-π between layer by layer is acted on, this will cause unavoidably
Reuniting effect, this will make the number of plies of graphene thicken, influences its electric conductivity.Therefore two-dimensional graphene is applied to a certain degree
On be restricted.Three-dimensional grapheme due to its relatively large specific surface area, exposed more active sites and quickly
Electronic transmission performance is better than two-dimensional graphene to a certain extent.
According to report before, 3,4,9,10- tetrabasic carboxylic acids (PTCA) can covalent and non-covalent modification graphene.Stone
Black alkene layer will be separated effectively by PTCA molecule, moreover it is possible to introduce more carboxyls after reduction.This not only makes graphene
Successfully removing, and effectively it can be modified.
Beta-cyclodextrin is a kind of polysaccharide being made of seven glucose units.Its inner cavity is hydrophobic, and exocoel is hydrophilic, ring paste
The inner cavity of essence can include different types of guest molecule, such as amino acid molecular, anion and cation guests and polymerization
Object chain etc., this has a wide range of applications cyclodextrin in electrochemical sensor.Beta-cyclodextrin (β-CD) is typically only capable to letter
A single surface for being compounded in material.Amidized β-CD has and can carry out with the carboxyl on 3,4,9,10- tetrabasic carboxylic acid
Covalent linkage makes it possible to largely connect amidized β-CD and amidized β-CD has a large amount of chiral acti ve sites.Therefore
By NH2- β-CD and the graphene of PTCA functionalization are combined with each other by amido bond and are expected to be widely applied to electrochemical sensor.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of amination β-CD/PTCA functionalization graphene composite material.
One, the preparation of amination β-CD/PTCA functionalization graphene composite material
(1) preparation of PTCA functionalization graphene rGO-PTCA: graphene oxide GO ultrasound is dispersed in water, is added 3,
4,9,10- tetrabasic carboxylic acids (PTCA) continue 2.5 ~ 3.0h of ultrasound；35 ~ 45 DEG C are then heated to, 24 ~ 25h is continuously vigorously stirred
(mixing speed is 500 ~ 700rpm)；It is added after ammonia spirit adjusts pH=11 ~ 12 and adds hydrazine hydrate, reacted at 90 ~ 95 DEG C
3.0 ~ 3.5 h are filtered, and are washed, dry, obtain rGO-PTCA.
The mass ratio of graphene oxide GO and PTCA are 1:1.5 ~ 1:2.0；The additional amount of hydrazine hydrate is graphene oxide GO
The 0.1% ~ 0.3% of quality.
(2) preparation of rGO-PTCA-CD: rGO-PTCA composite material being distributed in water and forms uniform dispersion, Xiang Qi
Middle addition NH2After mixing, EDC and NHS is added as crosslinking agent in-β-CD, stops instead after being stirred to react 48 ~ 49h at room temperature
It answers, filtering (filtering uses 0.2 μm of filter membrane), washing obtains composite material rGO-PTCA-CD.
PTCA functionalization graphene rGO-PTCA(rGO-PTCA) and amination β-CD(NH2- β-CD) mass ratio be 2:1
~2.5:1；The additional amount of EDC is 2 ~ 2.5 times of amination β-CD quality；The additional amount of NHS is PTCA functionalization graphene rGO-
3 ~ 3.5 times of PTCA mass.
Two, the characterization of amination β-CD/PTCA functionalization graphene composite material
1, infrared spectrum
Fig. 1 is NH2- β-CD, rGO-PTCA and rGO-PTCA-CD infrared spectrogram.NH2- β-CD is in 3408 cm-1Place is shown
The stretching vibration peak of NH/OH, in 1158 cm-1The peak of C-N is presented in place, in 2925 cm-1Show CH2Peak, the peak of C-O exists
1034 cm-1.In the FT-IR spectrogram of rGO-PTCA, the stretching vibration of C=O is in 1692 cm-1.For rGO-PTCA-CD composite wood
Material, it appear that and NH2Peak-β-CD similar with rGO-PTCA appears in 3418 cm-1、2965 cm-1、1693 cm-1、
1255 cm-1, it is respectively belonging to O-H/N-H, CH2, C=O and C-N stretching vibration peak, illustrate amination β-CD/PTCA functionalization
The compound success of graphene.
2, scanning electron microscope (SEM) photograph
Fig. 2 is the scanning electron microscope (SEM) photograph of rGO-PTCA and rGO-PTCA-CD.In rGO-PTCA as can be seen that it has typical three
Structure and empty structure are tieed up, this is beneficial to the transmission of electronics.RGO-PTCA-CD has biggish surface area, this is conducive to
The load of guest molecule and the transmission of electronics.
Three, rGO-PTCA-CD electrochemical property test
1, the preparation of modified electrode
Composite material rGO-PTCA-CD is evenly spread in water and forms the dispersion liquid that concentration is 1 ~ 1.2mg/mL, then will
RGO-PTCA-CD dispersant liquid drop is coated in the surface processed glass-carbon electrode (GCE), is built into rGO-PTCA-CD/GCE.
2, the chemical property of modified electrode
By electrode rGO-PTCA/GCE, NH2- β-CD/GCE and rGO-PTCA-CD/GCE immerses 5 mM Fe (CN) respectively6 4−/3−
Comprising 0.1 M KCl as supporting electrolyte, in scanning potential from -0.2V to 0.6 V and 5 mM solution of ferrocene Fc
(vH2O/vEt2O=1:1) it include 0.1 M KCl as supporting electrolyte scanning from -0.4 to 0.7 V of potential, sweeping speed is 0.05
V/s.Its chemical property is surveyed with cyclic voltammetry.The CV curve of different modifying electrode is as shown in figs.3 a and 3b.By Fig. 3 A and 3B
As can be seen that the size of peak current is followed successively by rGO-PTCA/GCE > rGO-PTCA-CD/GCE > GCE > NH2-β-CD/GCE。
Work as NH further, it is also possible to observe2- β-CD/GCE immerses 5 mM solution of ferrocene Fc (vH2O/vEt2O=1:1)
When comprising 0.1 M KCl, compared to bare electrode, peak current reduction is not it is obvious that this is because the cavity of Fc is just pasted with ring
The cavity size matching of essence, in addition, cyclodextrin inner chamber is hydrophobic, Fc also has hydrophobicity.Fe(CN)6 4−/3−With hydrophily, and ring
Dextrin inner cavity be it is hydrophobic, its size is also bigger than cyclodextrin, therefore, Fe (CN)6 4−/3−It not can enter cyclodextrin cavity
Redox reaction.Similar phenomenon can be observed on rGO-PTCA-CD/GCE.
In conclusion the present invention is first acted on graphene oxide (GO) with 3,4,9,10- tetrabasic carboxylic acids (PTCA) by π-π
Removing, reduces GO reuniting effect due to caused by pi-pi accumulation, increases the interlamellar spacing of GO, obtain the GO-PTCA of functionalization,
Under the conditions of again existing for the ammonium hydroxide and hydrazine hydrate, GO-PTCA is restored, rGO-PTCA is obtained；Then using EDC and NHS as
Crosslinking agent makes NH2Composite material is made by amido bond covalent bonding in the carboxyl on amino and rGO-PTCA on-β-CD
RGO-PTCA-CD, the composite material have better electronic transmission performance, can be applied to pass for supercapacitor, electrochemistry
The fields such as sensor, lithium ion battery, nano material and hydrogen storage.
Detailed description of the invention
Fig. 1 is the infrared spectrum of the composite material of the graphene bridging 3,4,9,10- tetrabasic carboxylic acid of beta-cyclodextrin functionalization.
Fig. 2 is rGO-PTCA(A) and scanning electron microscope (SEM) photograph rGO-PTCA-CD(B).
Fig. 3 is Fe (CN)6 4−/3−(A) and Fc(B) in the cyclic voltammetry curve of different modifying electrode.
Specific embodiment
Below by specific embodiment to the graphene bridging 3,4,9,10- tetrabasic carboxylic acid of beta-cyclodextrin functionalization of the present invention
The preparation method of composite material be described further.
(1) preparation of PTCA functionalization graphene (rGO-PTCA): 100g graphene oxide is evenly dispersed by ultrasound
In 50mL water；150mgPTCA is added, continues ultrasound 3.0h；Then mixed liquor is warming up to 40 DEG C, continuous acutely (stirring speed
Degree is 500 ~ 700rpm) it stirs for 24 hours, 500 μ L ammonia spirits (adjusting pH=11 ~ 12) and 200 μ L hydrazine hydrates are added, at 90 ~ 95 DEG C
3.0h is reacted, is filtered, is washed, it is dry, obtain rGO-PTCA.
(2) preparation of rGO-PTCA-CD: 50mg rGO-PTCA composite material is distributed to be formed in 50mL water and is uniformly divided
Dispersion liquid；By 20mg NH2- β-CD is added thereto and is uniformly mixed, then be added 50mg EDC and 150mg NHS as amino with
The crosslinking agent of carboxy amidation reaction stops reaction after stirring 48h at room temperature, and filtering (filtering uses 0.2 μm of filter membrane) is washed
It washs, obtains rGO-PTCA-CD composite material.
In above-described embodiment, the raw material and drug being related to are commercially available, wherein NH2- β-CD(CAS:29390-67-8)
From Shandong Binzhou Zhi Yuan Biotechnology Co., Ltd.
Claims (8)
1. a kind of preparation method of amination β-CD/PTCA functionalization graphene composite material, including following technique:
(1) preparation of PTCA functionalization graphene rGO-PTCA: graphene oxide GO ultrasound is dispersed in water, is added 3,
4,9,10- tetrabasic carboxylic acids continue 2.5 ~ 3.0h of ultrasound；35 ~ 45 DEG C are then heated to, 24 ~ 25h is continuously vigorously stirred；Ammonia is added
Aqueous solution adds hydrazine hydrate after adjusting pH=11 ~ 12, in 90 ~ 95 DEG C of 3.0 ~ 3.5 h of reaction, filters, washs, dry, obtains
rGO-PTCA；
(2) NH2The preparation of-β-CD/rGO-PTCA: rGO-PTCA composite material being distributed in water and forms uniform dispersion, to
NH is wherein added2- β-CD after mixing, is added EDC and NHS as crosslinking agent, stops after being stirred to react 48 ~ 49h at room temperature
Reaction is filtered, and washing obtains composite material rGO-PTCA-CD.
2. a kind of preparation method of amination β-CD/PTCA functionalization graphene composite material as described in claim 1, feature
Be: in step (1), the mass ratio of the graphene oxide GO and PTCA is 1:1.5 ~ 1:2.0.
3. a kind of preparation method of amination β-CD/PTCA functionalization graphene composite material as described in claim 1, feature
Be: in step (1), the additional amount of hydrazine hydrate is the 0.1% ~ 0.3% of graphene oxide GO mass.
4. a kind of preparation method of amination β-CD/PTCA functionalization graphene composite material as described in claim 1, feature
Be: in step (1), continuing vigorous mixing speed is 500 ~ 700rpm.
5. a kind of preparation method of amination β-CD/PTCA functionalization graphene composite material as described in claim 1, feature
It is: in step (2), PTCA functionalization graphene rGO-PTCA(rGO-PTCA) and amination β-CD(NH2- β-CD) quality
Than for 2:1 ~ 2.5:1.
6. a kind of preparation method of amination β-CD/PTCA functionalization graphene composite material as described in claim 1, feature
Be: in step (2), the additional amount of EDC is 2 ~ 2.5 times of amination β-CD quality.
7. a kind of preparation method of amination β-CD/PTCA functionalization graphene composite material as described in claim 1, feature
Be: in step (2), the additional amount of NHS is 3 ~ 3.5 times of PTCA functionalization graphene rGO-PTCA mass.
8. a kind of preparation method of amination β-CD/PTCA functionalization graphene composite material as described in claim 1, feature
Be: in step (2), filtering uses 0.2 μm of filter membrane.
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